Substituted 4-hetaryl-pyrazolines as pest control agents

ABSTRACT

The present invention relates to novel substituted pyrazolines of the formula (I) 
     
       
         
         
             
             
         
       
         
         
           
             in which R 1 , R 2 , R 3  and R 4  are as defined in the disclosure, to a plurality of processes for preparing these substances and their use for controlling pests, and to novel intermediates and processes for their preparation.

The present patent application has been filed under 35 U.S.C. 371 as a national stage application of PGT/EP03/00811, filed Jan. 28,2003 which was published in German as International Patent Publication WO 03/066625 on Aug. 14, 2003, which is entitled to the right of priority of German Patent Application 102 05 057.0, filed Feb. 7, 2002.

The present invention relates to novel substituted 4-hetarylpyrazolines, to processes for their preparation and to their use as pesticides.

It is known that certain substituted pyrazolines have insecticidal and acaricidal properties (cf., for example, DE-A 44 16 112, EP-A 0 679 644 or EP-A 0 438 690). However, the activity of these compounds is, in particular at low active compound concentrations and application rates, not always entirely satisfactory.

This invention provides novel substituted 4-hetarylpyrazolines of the formula (I)

in which

-   R¹ represents in each case optionally substituted oxadiazolyl,     thiadiazolyl or tetrazolyl,

R² represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl or cyano,

-   R³ represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio,     haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl or cyano and -   R⁴ represents hydrogen, cyanomethyl or alkoxycarbonyl.

Depending on the nature and number of substituents, the compounds of the formula (I) may be present as geometrical and/or optical isomers, regioisomers and/or configurational isomers, or as mixtures of these isomers of varying composition. What is claimed by the invention are both the pure isomers and the isomer mixtures. Furthermore, it has been found that the substituted 4-hetarylpyrazolines of the formula (I) are obtained when

-   a) pyrazolines of the formula (II)

-   -   in which     -   R¹ and R² are as defined above     -   are reacted with isocyanates of the formula (III)

-   -   in which     -   R³ is as defined above,     -   if appropriate in the presence of a diluent and if appropriate         in the presence of a catalyst;         and

-   b) the pyrazoline derivatives of the formula (Ia) according to the     invention obtained in this manner

-   -   in which     -   R¹, R² and R³ are as defined above     -   are, if appropriate, reacted with halides of the formula (IV)         Hal¹-R⁴  (IV)     -   in which     -   R⁴ is as defined above and     -   Hal¹ represents halogen,     -   if appropriate in the presence of a diluent and if appropriate         in the presence of a base; or

-   c) anilines of the formula (V)

-   -   in which     -   R³ and R⁴ are as defined above     -   are initially reacted with phosgene in the presence of a diluent         and, if appropriate, in the presence of a base, and the         resulting carbamoyl chlorides of the formula (VI)

-   -   in which     -   R³ and R⁴ are as defined above     -   are, directly or after intermediate isolation, reacted with         pyrazolines of the formula (II)

-   -   in which     -   R¹ and R² are as defined above     -   in the presence of a diluent and, if appropriate, in the         presence of a base.

Finally, it has been found that the novel substituted 4-hetarylpyrazolines of the formula (I) have highly pronounced biological properties and are suitable in particular for controlling animal pests, in particular insects, arachnids and nematodes encountered in agriculture, in forests, in the protection of stored products and the protection of materials and in the hygiene sector.

The formula (I) provides a general definition of the 4-hetarylpyrazolines according to the invention.

Preferred substituents or ranges of the radicals listed in the formulae mentioned above and below are illustrated below:

-   R¹ preferably represents in each case optionally substituted     oxadiazolyl or thiadiazolyl, exemplary substituents being:     optionally substituted alkyl, optionally substituted alkoxy,     optionally substituted alkylthio, optionally substituted aryl or     optionally substituted arylalkyl;     -   and also represents optionally substituted tetrazolyl, exemplary         substituents being: optionally substituted alkyl, in each case         optionally substituted alkylthio or alkylsulphonyl, in each case         optionally substituted aryl or arylalkyl or optionally         substituted cycloalkyl. -   R² preferably represents fluorine, chlorine, bromine, iodine;     C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,     C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphinyl,     C₁-C₄-haloalkylsulphonyl or cyano. -   R³ preferably represents fluorine, chlorine, bromine, iodine;     C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,     C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,     C₁-C₄-haloalkylsulphonyl or cyano. -   R⁴ preferably represents hydrogen, cyanomethyl or     C₁-C₄-alkoxy-carbonyl. -   R¹ particularly preferably represents in each case optionally     substituted oxadiazolyl or thiadiazolyl, exemplary substituents     being: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,     C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, and also phenyl or benzyl,     each of which is optionally mono- to trisubstituted by identical or     different substituents from the group consisting of halogen,     C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy;     -   and also represents optionally substituted tetrazolyl, exemplary         substituents being: C₁-C₄-alkyl, C₁-C₄-haloalkyl,         C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl, furthermore phenyl or         benzyl, each of which is optionally mono- to trisubstituted by         identical or different substituents from the group consisting of         halogen, C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy, furthermore         cyclopentyl or cyclohexyl, each of which is optionally mono- to         trisubstituted by identical or different substituents from the         group consisting of C₁-C₄-alkyl. -   R² particularly preferably represents fluorine, chlorine, bromine,     iodine, cyano; C₁-C₂-alkylthio, C₁-C₂-alkylsulphonyl and also     C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy; C₁-C₂-haloalkylthio or     C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or     different halogen atoms from the group consisting of fluorine,     chlorine and bromine. -   R³ particularly preferably represents chlorine, bromine, iodine,     cyano; and also represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,     C₁-C₂-haloalkylthio, C₁-C₂-haloalkylsulphinyl or     C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or     different halogen atoms from the group consisting of fluorine,     chlorine and bromine. -   R⁴ particularly preferably represents hydrogen, cyanomethyl or     C₁-C₄-alkoxy-carbonyl. -   R¹ very particularly preferably represents the thiadiazolyls and     oxadiazolyls below:

-   -   where     -   X¹ and X² independently of one another represent hydrogen,         C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio,         C₁-C₄-haloalkylthio and also represent phenyl or benzyl, each of         which is optionally mono- to trisubstituted by identical or         different substituents from the group consisting of halogen,         C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having in each case 1 to 3         identical or different halogen atoms from the group consisting         of fluorine, chlorine and bromine;     -   and also represents the following tetrazolyls:

-   -   where     -   X³ and X⁴ independently of one another represent hydrogen,         C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical or         different halogen atoms from the group consisting of fluorine,         chlorine and bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl,         represent phenyl or benzyl, each of which is optionally mono- to         trisubstituted by identical or different substituents from the         group consisting of halogen, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy         having in each case 1 to 3 identical or different halogen atoms         from the group consisting of fluorine, chlorine and bromine, and         also represent cyclopentyl or cyclohexyl, each of which is         optionally mono- to trisubstituted by C₁-C₄-alkyl.

-   R² very particularly preferably represents fluorine, chlorine,     bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or     trifluoromethylthio.

-   R³ very particularly preferably represents chlorine, bromine,     iodine, cyano; trifluoromethyl, trifluoromethoxy,     trifluoromethylthio, trifluoromethyl-sulphinyl or     trifluoromethylsulphonyl.

-   R⁴ very particularly preferably represents hydrogen, cyanomethyl,     methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl or n-, i-,     s- or t-butoxycarbonyl.

-   R¹ especially preferably represents the thiadiazolyls and     oxadiazolyls below:

-   -   where     -   X¹ and X² independently of one another represent hydrogen;         methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,         trifluoromethyl, trifluoromethoxy or trifluoromethylthio and         also represent phenyl or benzyl, each of which is optionally         mono- or disubstituted by identical or different substituents         from the group consisting of fluorine, chlorine, bromine,         trifluoromethyl and trifluoromethoxy;     -   and also represents the following tetrazolyls:

-   -   where     -   X³ and X⁴ independently of one another represent hydrogen;         methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl;         fluoromethyl, difluoromethyl, trifluoro-methyl,         1,1-difluoroethyl, 2,2,2-trifluoroethyl, methylthio, ethylthio,         methylsulphonyl, ethylsulphonyl; represent phenyl or benzyl,         each of which is optionally mono- or disubstituted by identical         or different substituents from the group consisting of fluorine,         chlorine, bromine, methyl, methoxy, trifluoromethyl and         trifluoromethoxy, and also represent cyclohexyl which is         optionally mono- or disubstituted by methyl.

-   R² especially preferably represents fluorine, chlorine, bromine,     iodine, methylthio, trifluoromethyl, trifluoromethoxy or     trifluoromethylthio.

-   R³ especially preferably represents chlorine, bromine, iodine,     cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,     trifluoromethyl-sulphinyl or trifluoromethylsulphonyl.

-   R⁴ especially preferably represents hydrogen or cyanomethyl.

Very particular preference is furthermore given to compounds of the formula (I) in which R¹ represents optionally substituted tetrazolyl, possible substituents being: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl, furthermore phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents from the group consisting of halogen, C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy, furthermore cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different C₁-C₄-alkyl.

Very particular preference is furthermore given to compounds of the formula (I) in which R² represents chlorine.

Very particular preference is furthermore given to compounds of the formula (I) in which R⁴ represents hydrogen.

Very particular preference is furthermore given to compounds of the formula (I) in which R⁴ represents cyanomethyl.

Very particular preference is furthermore given to compounds of the formula (I) in which R³ represents trifluoromethoxy or trifluoromethylthio.

The abovementioned general or preferred radical definitions or illustrations apply to the end products and, correspondingly, to starting materials and intermediates. These radical definitions can be combined with one another as desired, i.e. including combinations between the respective preferred ranges.

Preference according to the invention is given to compounds of the formula (I) which contain a combination of meanings listed above as being preferred (preferable).

Particular preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.

Very particular preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.

Special preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being especially preferred.

In the radical definitions given above and below, hydrocarbon radicals, such as alkyl, are in each case straight-chain or branched as far as this is possible—including in combination with heteroatoms such as alkoxy.

Using, for example, 3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1H-pyrazole and 4-trifluoromethoxyphenyl isocyanate as starting materials, the course of the process (a) according to the invention can be represented by the formula scheme below:

Using, for example, N-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1-pyrazolcarboxanilide and bromacetonitrile as starting materials, the course of the reaction of the process (b) according to the invention can be represented by the following formula scheme:

Using, for example, N-cyanomethyl-4-trifluoromethoxyaniline, phosgene and 3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole as starting materials, the course of the process (c) according to the invention can be represented by the following formula scheme:

The formula (II) provides a general definition of the pyrazolines to be used as starting materials for carrying out the processes (a) and (c) according to the invention. In this formula, R¹ and R² preferably, particularly preferably, very particularly preferably and especially preferably have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred, particularly preferred, very particularly preferred and especially preferred for these radicals.

The pyrazolines of the formula (II) are novel and also form part of the subject-matter of this application. They are obtained by reacting substituted acetophenones of the formula (VII)

in which

-   R¹ and R² are as defined above -   in a first step with known bis-dialkylaminomethanes of the formula     (VII)     (Alk)₂N—CH₂—N(Alk)₂  (VIII)     in which -   Alk represents C₁-C₄-alkyl, preferably methyl, -   in the presence of an inert organic solvent (preferably a     halogenated hydrocarbon, such as, for example, methylene chloride or     ethylene chloride) at temperatures between 0° C. and 120° C.,     preferably between 20° C. and 80° C. (cf., for example, EP-A 0 546     420), and, if appropriate, isolating the resulting dialkylaminoalkyl     ketones of the formula (IX)

in which

-   R¹, R² and Alk are as defined above -   and reacting these in a second step with hydrazine (hydrate) in the     presence of an inert organic solvent (preferably an alcohol, such     as, for example, methanol or ethanol) at temperatures between 0° C.     and 80° C., preferably between 20° C. and 50° C. (cf. also the     Preparation Examples).

Some of the substituted acetophenones of the formula (VII) are known (cf., for example, Chemiker-Zeitung 1989, 113, 217-219; Synthesis 1988, 453-55; J. Chem. Soc., Perkin Trans. 1 1986, 1157-63; Chemiker-Zeitung 1985, 109, 432-433 and WO 99/08678) and/or they can be obtained in a generally known manner.

Thus, for example, the acetophenones of the formula (VIIa)

in which

-   R² and X⁴ are as defined above -   can be obtained by reacting haloacetophenones of the formula (X)

in which

-   R² is as defined above and -   Hal² represents halogen, preferably chlorine or bromine, -   with tetrazoles of the formula (XI)

in which

-   X⁴ is as defined above     in the presence of an organic or inorganic base (for example     potassium carbonate) and, if appropriate, in the presence of an     inert organic solvent (for example acetonitrile) at temperatures     between 0° C. and 100° C., preferably between 20° C. and 80° C. (cf.     also the Preparation Examples).

The haloacetophenones of the formula (X) and the tetrazoles of the formula (XI) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

Acetophenones of the Formula (VII b)

in which

-   R² and X³ are as defined above -   can be obtained by reacting 2-cyanoacetophenones of the formula     (XII)

in which

-   R² is as defined above -   with sodium azide and amine hydrochloride (for example triethylamine     hydrochloride) in the presence of an inert solvent (for example     acetonitrile, dimethylformamide, toluene), preferably under reflux     (cf. also the Preparation Examples) and, if appropriate, reacting     the resulting acetophenones of the formula (VII c)

in which

-   R² is as defined above -   with compounds of the formula (XIII)     E-X³⁻¹  (XII)     in which -   X³⁻¹ represents C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical     or different halogen atoms from the group consisting of fluorine,     chlorine and bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl,     represents phenyl or benzyl, each of which is optionally mono- to     trisubstituted by identical or different substituents from the group     consisting of halogen, C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having     in each case 1 to 3 identical or different halogen atoms from the     group consisting of fluorine, chlorine and bromine, and also     represents cyclopentyl or cyclohexyl, each of which is optionally     mono- to trisubstituted by C₁-C₄-alkyl, and -   E represents an anionic leaving group, preferably chlorine, bromine,     iodine, acetoxy, tosyl or mesyl -   in the presence of an organic or inorganic base (for example     potassium carbonate) and, if appropriate, in the presence of an     inert organic solvent (for example acetonitrile) at temperatures     between 0° C. and 80° C., preferably between 10° C. and 50° C. (cf.     also the Preparation Examples).

When preparing acetophenones of the formula (VIIb) in which X³ represents a tertiary alkyl radical, it is in some cases advantageous to react the acetophenones of the formula (VIIc) with tertiary alcohols in the presence of strong acids, such as, for example, trifluoroacetic acid and/or sulphuric acid.

The 2-cyanoacetophenones of the formula (XII) and the compounds of the formula (XIII) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

The Acetophenones of the Formula (VII d)

in which

-   R² and X¹ are as defined above -   can be obtained by reacting ethyl benzoates of the formula (XIV)

in which

-   R² is as defined above -   with methylthiadiazoles of the formula (XV)

in which

-   X¹ is as defined above -   in the presence of a strong base (for example sodium hydride or     tert-butyllithium) in the presence of an inert organic solvent (for     example toluene), preferably under reflux (cf. also Chemiker-Zeitung     1989, 113, 217-219).

Acetophenones having other thiadiazolyl radicals can be obtained in a corresponding manner.

The ethyl benzoates of the formula (XIV) and the methylthiadiazoles of the formula (XV) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

The Acetophenones of the formula (VII e)

in which

-   R² and X² are as defined above -   can be obtained by refluxing amidoximes of the formula (XVI)

in which

-   R² is as defined above -   in a customary manner with appropriate X²-substituted acetic acid     derivatives, such as, preferably alkyl esters or anhydrides.

The amidoximes of the formula (XVI) can be obtained in a generally known manner by reacting 2-cyanoacetophenones of formula (XII) or ketals thereof with hydroxylamine hydrochloride in the presence of a base (for example potassium carbonate).

The acetophenones of the formula (VII f)

in which

-   R² and X² are as defined above -   can be obtained by refluxing hydrazides of the formula (XVII)

in which

-   R² is as defined above -   in a customary manner with appropriate X²-substituted acetic acid     derivatives, such as, preferably, alkyl esters, also in the form of     corresponding ortho esters.

The hydrazides of the formula (XVII) can be obtained in a generally known manner by reacting corresponding ester derivatives with hydrazine.

The acetophenones of the formula (VII g)

in which

-   R² and X² are as defined above -   can be obtained by refluxing esters of the formula (XVIII)

in which

-   R² and Alk are as defined above -   in a customary manner with amidoximes of the formula (XIX)

in which

-   X² is as defined above.

The esters of the formula (XVIII) and the amidoximes of the formula (XIX) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

The formula (III) provides a general definition of the isocyanates further to be used as starting materials in the process (a) according to the invention. In this formula, R³ preferably, particularly preferably, very particularly preferably and especially preferably has those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred, particularly preferred, very particularly preferred and especially preferred for this radical.

The isocyanates of the formula (III) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

The formula (IV) provides a general definition of the halides to be used as starting materials for carrying out the process (b) according to the invention. In this formula, R⁴ preferably, particularly preferably, very particularly preferably and especially preferably has those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred, particularly preferred, very particularly preferred and especially preferred for this radical. Hal¹ preferably represents chlorine or bromine.

The halides of the formula (IV) are generally known compounds of organic chemistry.

The formula (V) provides a general definition of the anilines to be used as starting materials for carrying out the process (c) according to the invention. In this formula, R³ and R⁴ preferably, particularly preferably, very particularly preferably and especially preferably have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred, particularly preferred, very particularly preferred and especially preferred for these radicals.

The anilines of the formula (V) are generally known compounds of organic chemistry and/or can be obtained in a generally known manner.

The process (a) according to the invention is preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether, dibutyl ether, methyl tert-butyl ether, methyl tert-amyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, esters, such as methyl acetate or ethyl acetate, nitriles, such as, for example, acetonitrile or propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone or hexamethyl phosphoric triamide.

The process (a) according to the invention is preferably also carried out using a catalyst. Suitable catalysts are in particular tertiary organic amines, such as, for example, triethylamine.

The reaction temperatures in the process (a) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 120° C., preferably at temperatures between 20° C. and 80° C.

The process (a) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

For carrying out the process (a) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively small excess of one of the two components employed. Work-up is carried out by customary methods (cf. the Preparation Examples).

The processes (b) and (c) according to the invention are preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether, dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, esters, such as methyl acetate or ethyl acetate, nitriles, such as, for example, acetonitrile or propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone or hexamethyl phosphoric triamide.

Suitable bases for carrying out the processes (b) and (c) according to the invention are all acid binders which are customarily used for such reactions. Preferred are alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride or calcium hydride; alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; alkali metal and alkaline earth metal carbonates or bicarbonates, such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or calcium carbonate; alkali metal acetates, such as sodium acetate or potassium acetate, alkali metal alcohols, such as sodium tert-butoxide or potassium tert-butoxide; further basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methylpyridine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]-octane (DABCO).

The reaction temperatures in the process (b) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 120° C., preferably at temperatures between 20° C. and 80° C.

The process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

For carrying out the process (b) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ an excess of halide and base. Work-up is carried out by customary methods (cf. the Preparation Examples).

The reaction temperatures in the process (c) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −10° C. and 120° C., preferably at temperatures between 0° C. and 100° C.

The process (c) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

For carrying out the process (c) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ an excess of chloride and base. Work-up is carried out by customary methods (cf. the Preparation Examples).

The active compounds, according to the invention, having good plant tolerance and favourable warm-blood toxicity, are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably used as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepiisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. and Schistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp. and Damalinia spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi and Frankliniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofinannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrus oryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp., Derrnanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus spp.

The compounds according to the invention can be used with particularly good results for controlling plant-damaging insects, such as, for example, against caterpillars of the cotton bud worm (Heliothis virescens and Heliothis armigera), the larvae of the mustard beetle (Phaedon cochliariae), the eggs and/or larvae and caterpillars of the diamondback moth (Plutella xylostella) and the caterpillars of the army worm (Spodoptera exigua and Spodoptera frugioerda).

At certain concentrations or application rates, the compounds according to the invention may, if appropriate, also be used as herbicides and microbicides, for example as fungicides, antimycotics and bactericides. If appropriate, they may also be used as intermediates or precursors for the synthesis of further active compounds.

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (inclusive of naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, inclusive of the transgenic plants and inclusive of the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and also water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be employed as such or in their formulations as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, for example in order to increase the activity spectrum or avoid the development of resistance. In many cases synergistic effects are achieved, ie. the efficacy of the mixture is greater than the efficacy of the individual components.

Suitable examples of co-components in mixtures are the following compounds:

Fungicides:

aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine, azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, carpropamid, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, iprovalicarb, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB), quinoxyfen

sulphur and sulphur preparations, spiroxamine,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, trifloxystrodin, triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705, OK-8801,

-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol, -   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol, -   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol, -   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol, -   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone, -   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, -   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime, -   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione, -   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione, -   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene, -   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole, -   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole, -   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole, -   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol, -   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide, -   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate, -   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, -   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, -   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole, -   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole, -   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile, -   2-aminobutane, -   2-bromo-2-(bromomethyl)-pentanedinitrile, -   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide, -   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide, -   2-phenylphenol (OPP), -   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione, -   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide, -   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile, -   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine, -   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide, -   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one, -   8-hydroxyquinoline sulphate, -   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, -   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, -   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, -   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethylmorpholinehydrochloride, -   ethyl [(4-chlorophenyl)-azo]-cyanoacetate, -   potassium hydrogen carbonate, -   methanetetrathiol sodium salt, -   methyl     1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate, -   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, -   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate, -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide, -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide, -   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide, -   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine, -   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine, -   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, -   N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide, -   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide, -   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide, -   N-formyl-N-hydroxy-DL-alanine sodium salt, -   O,O-diethyl     [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, -   O-methyl S-phenyl phenylpropylphosphoramidothioate, -   S-methyl 1,2,3-benzothiadiazole-7-carbothioate, -   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran-3′-one -   4-[(3,4-dimethoxyphenyl)-3-(4-fluorophenyl)acryloyl]morpholine.     Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alphacypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, bistrifluron, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, dicofol, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, metaldehyde, methamidophos, metharhizium anisopliae, metharhizium flavoviride, methidathion, methiocarb, methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoate, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propargite, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep, sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, tetradifon, thetacypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazurone, trichlophenidine, trichlorfon, triflumuron, trimethacarb,

vamidothion, vaniliprole, Verticillium lecanii,

YI 5302,

zeta-cypermethrin, zolaprofos,

-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl     3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate, -   (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, -   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine, -   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole, -   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione, -   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide, -   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide, -   3-methylphenyl propylcarbamate, -   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene, -   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone, -   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone, -   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone, -   Bacillus thuringiensis strain EG-2348, -   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid, -   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl     butanoate, -   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide, -   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde, -   ethyl     [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate, -   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine, -   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide, -   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine, -   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide, -   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide, -   O,O-diethyl     [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, -   N-cyanomethyl-4-trifluoromethylnicotinamide, -   3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propoxy]benzene.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore be present when used as insecticides in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.

The compounds are employed in a customary manner appropriate for the use forms.

When used against hygiene pests and pests of stored products, the active compound is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetic Modified Organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions to be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are preferably treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized are in particular increased defence of the plants against insects by toxins formed in the plants, in particular those formed by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits that are also particularly emphasized are the increased defence of the plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars having these or still-to-be-developed genetic traits, which plants will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or the mixtures specifically mentioned in the present text.

The active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ectoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepiikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to the invention also have a strong insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned as examples and as being preferred—but without any limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus.

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus.

Bristletails, such as Lepiisma saccharina.

Industrial materials in the present context are to be understood as meaning non-living materials, such as, preferably, plastics, adhesives, sizes, papers and cards, leather, wood and processed wood products and coating compositions.

Wood and processed wood products are materials to be protected, especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agent according to the invention or mixtures comprising this are to be understood as meaning, for example:

building timber, wooden beams, railway sleepers, bridge components, boat jetties, wooden vehicles, boxes, pallets, containers, telegraph poles, wood panelling, wooden windows and doors, plywood, chipboard, joinery or wooden products which are used quite generally in house-building or in building joinery.

The active compounds according to the invention can be used as such, in the form of concentrates or in generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds according to the invention with at least one solvent or diluent, emulsifier, dispersing agent and/or binder or fixing agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments, and also other processing auxiliaries.

The insecticidal compositions or concentrates used for the preservation of wood and wood-derived timber products comprise the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on the nature and occurrence of the insects and on the medium. The optimum amount employed can be determined for the use in each case by a series of tests. In general, however, it is sufficient to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solvent or solvent mixture and/or an oily or oil-like organic chemical solvent or solvent mixture of low volatility and/or a polar organic chemical solvent or solvent mixture and/or water, and if appropriate an emulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-like solvents having an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C. Substances which are used as such oily or oil-like water-insoluble solvents of low volatility are appropriate mineral oils or aromatic fractions thereof, or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirit having a boiling range from 170 to 220° C., spindle oil having a boiling range from 250 to 350° C., petroleum and aromatics having a boiling range from 160 to 280° C., turpentine oil and the like, are advantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range from 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range from 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., can be replaced in part by organic chemical solvents of high or medium volatility, providing that the solvent mixture likewise has an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemical solvent or solvent mixture is replaced by an aliphatic polar organic chemical solvent or solvent mixture. Aliphatic organic chemical solvents containing hydroxyl and/or ester and/or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the present invention are the synthetic resins and/or binding drying oils which are known per se, are water-dilutable and/or are soluble or dispersible or emulsifiable in the organic chemical solvents employed, in particular binders consisting of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin, silicone resin, drying vegetable oils and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances can also be used as binders in an amount of up to 10% by weight. Dyestuffs, pigments, water-repelling agents, odour correctants and inhibitors or anticorrosive agents and the like which are known per se can additionally be employed.

It is preferred according to the invention for the composition or concentrate to comprise, as the organic chemical binder, at least one alkyd resin or modified alkyd resin and/or one drying vegetable oil. Alkyd resins having an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent evaporation of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acid esters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amyl stearate, oleates, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether or ketones, such as benzophenone or ethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organic chemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnation processes on a large industrial scale, for example vacuum, double vacuum or pressure processes.

The ready-to-use compositions can also comprise other insecticides, if appropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxide and triflumuron,

and also fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time be employed for protecting objects which come into contact with salt water or brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha group (goose barnacles), such as various Lepias and Scalpellum species, or by species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes species, increases the frictional drag of ships and, as a consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally frequent residence in dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by sessile Entomostraka groups, which come under the generic term Cirripedia (cirriped crustaceans), is of particular importance.

Surprisingly, it has now been found that the compounds according to the invention, alone or in combination with other active compounds, have an outstanding antifouling action.

Using the compounds according to the invention, alone or in combination with other active compounds, allows the use of heavy metals such as, for example, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zinc oxide, copper(I)ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides to be dispensed with, or the concentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionally comprise other active compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifouling compositions according to the invention are:

algicides such as

2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as

benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;

molluscicides such as

fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb;

or conventional antifouling active compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.

Moreover, the antifouling compositions according to the invention comprise the customary components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active compounds according to the invention, antifouling paints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/styrene/acrylonitrile rubbers, drying oils such as linseed oil, resin esters or modified hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.

If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which are preferably insoluble in salt water. Paints may furthermore comprise materials such as colophonium to allow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers, modifiers which affect the rheological properties and other conventional constituents. The compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products for controlling these pests alone or in combination with other active compounds and auxiliaries. They are active against sensitive and resistant species and against all development stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus and Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus and Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepiisma saccharina and Lepiismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa and Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. and Reticulitermes spp.

From the order of the Psocoptera, for example, Lepiinatus spp. and Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsylla cheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus and Triatoma infestans.

They are used in the household insecticides sector alone or in combination with other suitable active compounds such as phosphoric esters, carbamates, pyrethroids, growth regulators or active compounds from other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.

PREPARATION EXAMPLES Example 1

(Process a)

At 70° C., 1 g (5 mmol) of 4-trifluoromethylphenyl isocyanate is added to a mixture of 1.3 g (5 mmol) of 3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole, 0.1 ml of triethylamine and 50 ml of methyl tert-butyl ether. The mixture is stirred at 70° C. for 15 minutes and then allowed to slowly cool to room temperature. The solvent is then distilled off under reduced pressure and residue is purified by silica gel chromatography (methylene chloride/diethyl ether 5:1).

This gives 1.2 g (52% of theory) of N-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilide of logP (pH 2.3) 4.00.

Preparation of the Starting Material

At room temperature, 2.16 g (0.021 mol) of bisdimethylaminomethane are added to a solution of 5 g (0.02 mol) of 2-(5-methyltetrazol-2-yl)-4′-chloroacetophenone in 50 ml of methylene chloride, and the mixture is boiled at reflux for 18 hours. The solvent is then distilled off under reduced pressure and residue is dissolved in 50 ml of ethanol. 1.13 g (0.0226 mol) of hydrazine hydrate are added, and the reaction mixture is then stirred at 30° C. for 3 hours. The precipitated product is filtered off with suction and washed with a little cold ethanol and with water.

This gives 3.3 g (61% of theory) of 3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole of logP (pH 2.3)=2.11.

Preparation of the Precursor

A mixture of 17.5 g (0.075 mol) of 2-bromo-4′-chloroacetophenone, 6.3 g (0.075 mol) of 5-methyltetrazole, 12.4 g (0.09 mol) of potassium carbonate and 200 ml of acetonitrile is stirred at room temperature for 16 hours. The solvent is then distilled off under reduced pressure, about 200 ml of water are added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulphate and concentrated under reduced pressure.

This gives 17.5 g of a mixture of the two isomers 2-(5-methyltetrazol-2-yl)-4′-chloroacetophenone of logP (pH 2.3)=2.14 and 2-(5-methyltetrazol-1-yl)-4′-chloroacetophenone of logP (pH 2.3)=1.81. The target product is removed by silica gel chromatography (methylene chloride/ethyl acetate 10:1). This gives 6.3 g (35% of theory) of colourless crystals.

Example 2

(Process c)

At 0° C., 1.5 g (5.6 mmol) of N-cyanomethyl-N-(4-trifluoromethoxy)phenyl-carbamoyl chloride are added dropwise to a solution of 1.3 g (5 mmol) of 3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole and 0.84 ml (6 mmol) of triethylamine in 30 ml of methylene chloride, and the mixture is boiled under reflux for 3.5 hours. The mixture is then stirred at room temperature for 18 hours and then washed twice with in each case 100 ml of water. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. The residue is purified by silica gel chromatography (methylene chloride/diethyl ether 7:1).

This gives 1.7 g (68% of theory) of N-cyanomethyl-N-trifluoromethoxy-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilide of logP (pH 2.3)=3.68.

Preparation of the Starting Material

At 0° C., a solution of 20.7 g (0.0958 mol) of N-cyanomethyl-4-trifluoromethoxyaniline and 11.6 g (0.115 mol) of triethylamine in 150 ml of toluene is added to a solution of 10.4 g (0.105 mol) of phosgene in 100 ml of toluene, and the mixture is stirred at room temperature for 18 hours. Excess phosgene is then aspirated. The reaction mixture is washed twice with cold water, the organic phase is dried with sodium sulphate and the solvent is then distilled off under reduced pressure.

This gives 26.3 g (94% of theory) of N-cyanomethyl-N-(4-trifluoromethoxy)-phenylcarbamoyl chloride of refractive index n_(D) ²⁰=1.4816.

Example 3

(Process a)

At 70° C., 0.7 g (3 mmol) of 4-trifluoromethylphenyl isocyanate is added to a mixture of 0.8 g (3 mmol) of 3-(4-chlorophenyl)-4-(2-methyltetrazol-5-yl)-4,5-dihydro-1H-pyrazole, 0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether. The mixture is stirred at 70° C. for 15 minutes and then allowed to slowly cool to room temperature. The precipitated product is filtered off with suction.

This gives 1.2 g (52% of theory) of N-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilide of logP (pH 2.3)=4.25.

Preparation of the Starting Material

At room temperature, 1.6 g (0.016 mol) of bisdimethylaminomethane are added to a solution of 3.5 g (0.015 mol) of 2-(2-methyltetrazol-5-yl)-4′-chloroacetophenone in 50 ml of methylene chloride, and the mixture is boiled under reflux for 18 hours. The solvent is then distilled off under reduced pressure and the residue is dissolved in 50 ml of ethanol. 0.85 g (0.017 mol) of hydrazine hydrate is added, and the reaction mixture is then stirred at 30° C. for 3 hours. The solvent is then distilled off under reduced pressure at a bath temperature of at most 30° C., the residue is triturated with a little ethanol and the product is filtered off after crystallization and washed with ethanol and with water.

This gives 1.7 g (44% of theory) of 3-(4-chlorophenyl)-4-(2-methyltetrazol-5-yl)-4,5-dihydro-1H-pyrazole of logP (pH 2.3)=1.67.

Preparation of the Precursor

A mixture of 13 g (0.058 mol) of 2-tetrazol-5-yl-4′-chloroacetophenone, 9.7 g (0.07 mol) of potassium carbonate, 10 g (0.07 mol) of methyl iodide and 100 ml of acetonitrile is stirred at room temperature for 16 hours. The solvent is then distilled off under reduced pressure, about 200 ml of water are added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulphate and concentrated under reduced pressure.

This gives 12.2 g of a mixture of the two isomers 2-(2-methyltetrazol-5-yl)-4′-chloroacetophenone of logP (pH 2.3)=2.03 and 2-(1-methyltetrazol-5-yl)-4′-chloroacetophenone of logP (pH 2.3)=1.78. The target product is separated off by silica gel chromatography (methylene chloride/diethyl ether 3:1). This gives 3.5 g (21% of theory) of colourless crystals.

A mixture of 15 g (0.084 mol) of 2-cyano-4′-chloroacetophenone, 14.4 g (0.105 mol) of triethylamine hydrochloride, 6.9 g (0.105 mol) of sodium azide and 100 ml of toluene is boiled under reflux for 72 hours. The solvent is then distilled off under reduced pressure, the residue is dissolved in 200 ml of about 5% strength aqueous sodium hydroxide solution and insoluble particles are filtered off. Using dilute hydrochloric acid, the filtrate is adjusted to about pH 2 and the precipitated product is then filtered off with suction and washed with water. The crude product is dissolved in excess sodium bicarbonate solution, the solution is filtered and the filtrate is once more adjusted to about pH 2 using dilute hydrochloric acid. The precipitated product is filtered off and washed with water.

This gives 16.2 g (87% of theory) of 2-tetrazol-5-yl-4′-chloroacetophenone of logP (pH 2.3)=1.44.

Example 4

(Process a)

At 70° C., 1 g (5 mmol) of 4-trifluoromethoxyphenyl isocyanate is added to a mixture of 1.4 g (5 mmol) of 3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1H-pyrazole, 0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether. The mixture is stirred at 70° C. for 15 minutes and then allowed to slowly cool to room temperature. The solvent is then distilled off under reduced pressure and the residue is purified by silica gel chromatography (methylene chloride/diethyl ether 7:1).

This gives 0.15 g (6% of theory) of N-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilide of logP (pH 2.3)=3.77.

Preparation of the Starting Material

At room temperature, 1.9 g (0.0187 mol) of bisdimethylaminomethane is added to a solution of 4.5 g (0.018 mol) of 2-(2-methyl-1,3,4-thiadiazol-5-yl)-4′-chloroacetophenone (preparation see Chemiker-Zeitung 1989, 113, 217-219) in 50 ml of methylene chloride, and the mixture is boiled under reflux for 18 hours. The solvent is then distilled off under reduced pressure and the residue is dissolved in 50 ml of ethanol. 1 g (0.02 mol) of hydrazine hydrate is added, and the reaction mixture is then stirred at 30° C. for 3 hours. The solvent is then distilled off under reduced pressure at a bath temperature of at most 30° C., about 200 ml of water are added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulphate and concentrated under reduced pressure.

This gives 4.9 g (98% of theory) of 3-(4-chlorophenyl)-4-(2-methyl-1,3,4-thiadiazol-5-yl)-4,5-dihydro-1H-pyrazole of logP (pH 2.3)=1.77.

The compounds of the formula (I) listed in Table 1 below can be obtained analogously to Examples 1 to 4 and/or in accordance with the general statements on the preparation:

TABLE 1 (I)

Ex. R¹ R² R³ R⁴ logP (pH2.3) 5

Cl OCF₃ H 2.47 6

Br OCF₃ H 4.84 7

Br SCF₃ H 5.22 8

Cl OCF₃ H 3.86 9

Cl SCF₃ CH₂CN 3.94 10

Cl SCF₃ H 4.36 11

Cl SCF₃ H 4.16 12

Cl OCF₃ CH₂CN 3.42 13

Cl SCF₃ CH₂CN 3.68 14

Cl OCF₃ H 15

Cl SCF₃ H

The compounds of the formula (II) listed in Table 2 below can be obtained analogously to Examples 1, 3 and 4 and/or in accordance with the general statements on the preparation:

TABLE 2 (II)

Ex.No. R¹ R² logP (pH2.3) II-4

Cl 1.63 II-5

Br 2.74 II-6

Cl 1.54

The compounds of the formula (VII) listed in Table 3 below can be obtained analogously to Examples 1 and 3 and/or in accordance with the general statements on the preparation:

TABLE 3 (VII)

Ex.No. R¹ R² logP (pH2.3) VII-4

Cl 1.78 VII-5

Cl 1.79 VII-6

Br 3.19 VII-7

Cl 1.78

The logP values given in the tables and Preparation Examples above are determined in accordance with EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) using a reversed-phase column (C 18). Temperature: 43° C.

The determination is carried out in the acidic range at pH 2.3 using the mobile phases 0.1% aqueous phosphoric acid and acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration is carried out using unbranched alkan-2-ones (of 3 to 16 carbon atoms) with known logP values (determination of the logP values by retention times using linear interpolation between two successive alkanones).

The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES Example A

Heliothis armigera Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the cotton bud worm (Heliothis armigera) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compounds 2, 4 and 10 of the Preparation Examples, for example, show a kill of 100% after 7 days.

Example B

Heliothis virescens Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with Heliothis virescens caterpillars while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compound 1 of the Preparation Examples, for example, shows a kill of 100% after 7 days.

Example C

Phaedon larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the Preparation Examples, for example, show a kill of 100% after 7 days.

Example D

Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the diamondback moth (Plutella xylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compounds 1, 2, 4, and 10 of the Preparation Examples, for example, show a kill of 100% after 7 days.

Example E

Spodoptera exigua Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the army worm (Spodoptera exigua) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compounds 1, 2, 4, and 10 of the Preparation Examples, for example, show a kill of 100% after 7 days.

Example F

Spodoptera frugiperda Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm, the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the Preparation Examples, for example, show a kill of 100% after 7 days.

Example G

Plutella Test

Solvent:

-   -   100 parts by weight of acetone     -   1900 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with methanol to the desired concentration.

A stated amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed. After the methanol has evaporated, about 200-300 eggs of the diamondback moth (Plutella xylostella) are placed onto the feed.

After the desired period of time, the kill of the eggs and larvae is determined in %. 100% means that all animals have been killed; 0% means that none of the animals have been killed.

In this test, at an exemplary active compound concentration of 1000 ppm, compound 6 of the Preparation Examples, for example, shows a kill of 100% and compound 7 of the Preparation Examples a kill of 95%, in each case after 7 days.

Example H

Diabrotica balteata Test (Larvae in Soil)

Critical concentration test/soil insects—treatment of transgenic plants

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is mixed intimately with the soil. The concentration of the active compound in the preparation is virtually immaterial, only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/l) matters. The soil is filled into 0.25 1 pots, and these are left to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of the cultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed into each pot. After 2 days, the corresponding test insects are placed into the treated soil. After a further 7 days, the efficacy of the active compound is determined by counting the number of maize plants that have emerged (1 plant=20% activity).

Example I

Heliothis virescens Test (Treatment of Transgenic Plants)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade mark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the tobacco budworm caterpillar Heliothis virescens while the leaves are still moist.

After the desired period of time, the kill of the insects is determined. 100% means that all caterpillars have been killed, 0% means that none of the caterpillars have been killed. 

1. A substituted 4-hetarylpyrazoline of formula (I)

in which R¹ represents optionally substituted oxadiazolyl, thiadiazolyl, or tetrazolyl, R² represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl, or cyano, R³ represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl, or cyano, and R⁴ represents hydrogen, cyanomethyl, or alkoxycarbonyl.
 2. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R¹ represents optionally substituted oxadiazolyl or thiadiazolyl, wherein the substituents are optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl, or optionally substituted arylalkyl; or represents optionally substituted tetrazolyl, wherein the substituents are optionally substituted alkyl, optionally substituted alkylthio or alkylsulphonyl, optionally substituted aryl or arylalkyl, or optionally substituted cycloalkyl, R² represents fluorine, chlorine, bromine, iodine, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, or cyano, R³ represents fluorine, chlorine, bromine, iodine, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, or cyano, and R⁴ represents hydrogen, cyanomethyl, or C₁-C₄-alkoxy-carbonyl.
 3. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R¹ represents optionally substituted oxadiazolyl or thiadiazolyl, wherein the substituents are C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, or C₁-C₄-haloalkylthio or are phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy; or represents optionally substituted tetrazolyl, wherein the substituents are C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁-C₄-alkylsulphonyl, are phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy, or are cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of C₁-C₄-alkyl, R² represents fluorine, chlorine, bromine, iodine, cyano, C₁-C₂-alkylthio, or C₁-C₂-alkylsulphonyl; or represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy; C₁-C₂-haloalkylthio, or C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine, R³ represents chlorine, bromine, iodine, or cyano; or represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, C₁-C₂-haloalkylthio, C₁-C₂-haloalkylsulphinyl, or C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine, and R⁴ represents hydrogen, cyanomethyl, or C₁-C₄-alkoxy-carbonyl.
 4. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R¹ represents the thiadiazolyls or oxadiazolyls

 where X¹ and X² independently of one another represent hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁-C₄-haloalkylthio; or represent phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C₁-C₂-haloalkyl, and C₁-C₂-haloalkoxy having in each case 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; or represents the tetrazolyls

 where X³ and X⁴ independently of one another represent hydrogen; C₁-C₄-alkyl; C₁-C₂-haloalkyl having 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; C₁-C₄-alkylthio; C₁-C₄-alkylsulphonyl; phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C₁-C₂-haloalkyl, or C₁-C₂-haloalkoxy having in each case 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; or cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by C₁-C₄-alkyl, R² represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, R³ represents chlorine, bromine, iodine, cyano; trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, or trifluoromethylsulphonyl, and R⁴ represents hydrogen, cyanomethyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or n-, i-, s-, or t-butoxycarbonyl.
 5. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R¹ represents the thiadiazolyls or oxadiazolyls

 where X¹ and X² independently of one another represent hydrogen; methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio; or represent phenyl or benzyl, each of which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, trifluoromethyl, and trifluoromethoxy; or represents the tetrazolyls

 where X³ and X⁴ independently of one another represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl; fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulphonyl, or ethylsulphonyl; represent phenyl or benzyl, each of which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, and trifluoromethoxy; or represent cyclohexyl that is optionally mono- or disubstituted by methyl, R² represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, R³ represents chlorine, bromine, iodine, cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, or trifluoromethylsulphonyl, and R⁴ represents hydrogen or cyanomethyl.
 6. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R¹ represents optionally substituted tetrazolyl, wherein the substituents are C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁-C₄-alkylsulphonyl, are phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy, or are cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different C₁-C₄-alkyl.
 7. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R² represents chlorine.
 8. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R⁴ represents hydrogen.
 9. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R⁴ represents cyanomethyl.
 10. A substituted 4-hetarylpyrazoline of formula (I) according to claim 1 in which R³ represents trifluoromethoxy or trifluoromethylthio.
 11. A process for preparing a substituted 4-hetarylpyrazoline of formula (I) according to claim 1 comprising (a) reacting a pyrazoline of formula (II)

 in which R¹ and R² are as defined for formula (I) in claim 1, with an isocyanate of formula (III)

 in which R³ is as defined for formula (I) in claim 1, optionally in the presence of a diluent and optionally in the presence of a catalyst, thereby forming a pyrazoline derivative of formula (Ia) according to the invention

 in which R¹, R² and R³ are as defined for formula (I) in claim 1; and (b) optionally reacting the pyrazoline derivative of formula (Ia) with a halide of the formula (IV) Hal¹-R⁴  (IV)  in which  R⁴ is as defined for formula (I) in claim 1, and  Hal¹ represents halogen, optionally in the presence of a diluent and optionally in the presence of a base; or (c) initially reacting an aniline of formula (V)

 in which R³ and R⁴ are as defined for formula (I) in claim 1, with phosgene in the presence of a diluent and, optionally, in the presence of a base, to form a carbamoyl chloride of formula (VI)

 in which R³ and R⁴ are as defined for formula (I) in claim 1, and reacting the resultant carbamoyl chloride of formula (VI), directly or after isolation, with a pyrazoline of formula (II)

 in which R¹ and R² are as defined for formula (I) in claim 1, in the presence of a diluent and, optionally, in the presence of a base.
 12. A pesticide comprising one or more compounds of formula (I) according to claim 1 and one or more extenders and/or surfactants.
 13. A method for controlling pests comprising allowing an effective amount of one or more compounds of formula (I) according to claim 1 act on pests and/or their habitat.
 14. A process for preparing pesticides comprising mixing one or more compounds of formula (I) according to claim 1 with one or more extenders and/or surfactants. 